Coating composition and the vehicle therefor containing a compound of a clay and an onium base



Patented Dec. 23, 1952 UNITED STATES PATENT OFFICE COATING COMPOSITION AND THE VEHICLE THEREFOR. CONTAINING A COMPOUND OF A CLAY AND AN ONIUM BASE 19 Claims.

1 This invention relates to surface coatings and p-rocess of making the." same. A surface coating is a coating of the class comprising paints for the protection of wood and metal, and lacquers; and

printing inks. This application involves subject matter common with my abandoned application Serial No. 640,381, filed January 10, 1946 and is a continuation in part-of that application.

A paint generally comprises a pigment base,

such as white leadincorporated in avehicle-such as linseed oil, to which may beadded a drier ,or a thinner. Where such a paint" is supplied as a ready-mixed paint, the-pigment base is liable to settle, which is not desirable. A number of thickening or suspending agents have been pro posed and incorporated with the vehicle or with the pigment base and the-vehicle, but these generally have not beensatisfactory. A printing ink generally comprises an ink base such as carbon black incorporated in a vehicle such as a bodied linseed oil, or a synthetic resin, or avarnish, to which may be added driersand thinners, and

which is also-liable to'settling.

In many surface coatings, it is desirabl'e to exercise 'a control of the viscosity or thickening of the coating during the application. In the case of paint, this viscositycontrolshould be such that the: paint, following application, should not run or sag but should remain in place, as appliedby brushing, spraying or dipping; In the case of printing inks, where high speed presses are used and. where elevated. temperatures. are used. and

where elevated temperatures, are encountered on.

the. press and in the subsequent drying, it is desirablje that theink maintain its viscosity'at the elevated temperatures, so that it. willv not run or bleed prior. to drying. Thus another objective'is to provide av material for viscosity control.

One of the objects of this invention, therefore, is to provide a vehicle for a pigment base or for an ink base, containing a medium capable of imparting to the vehicle viscosity or thickening properties.

Another object of this invention isto provide a surface coatingcomprising a pigment base or an ink base suspended in an organic vehicle, together with a suspending agent ormedium, which will serveto effectively maintain the base in suspension.

Ahother object is to provide a process of making'such a-vehicle and such a surface coating.

Generally; stated and in accordance with il- T lustrative embodiments of this-invention, an orincorporated therewith aganio vehicle has medium or agent embodying a modified clay whichforms a. gel in the vehicle and has a substantial gel characteristic therein. A clay which is particularly useful for modification and for such incorporation is bentonite, including sodium and magnesium bentonites, which have particularly high base-exchange properties, traceable to their high percentage content of montmorillonite. Other clays may, however, be modified ashereinafter described for such employment.

The clays which are useful as starting materials in accordance with this invention are those exhibiting base-exchange properties, particularly those exhibiting; comparatively high base-exchange properties and containing cations capable of more or less easy replacement. The term clay, as used in the specification and the claims, includes montmorillonite, viz., sodium, potassium, lithium, and other bentonites, magnesium bentonite, sometimes called hectorite and saponite. Other clays found in nature are nontronite, attapulgite, illite, zeolites, fullers earth, particularly those of the Georgia-Florida type, hall'oysite, kaolinite, nacrite, and dickite. Clays, particularly those having high base-exchange capacities, as a result of certain structural atomic replacements, are believed to have negative charges which are normally neutralized by inorganic cations. As found in nature, therefore, they exist as salts of the weak clay-acids with bases such as the alkalior alkaline-earth metal hydroxides.

The base-exchange capacities of the various clays enumerated run from a low of about 3 to a high of about 100, based upon milliequivalents of exchangeable base per 100 grams of clay. Montmorillonite has comparatively high base-exchange capacities, viz., 60-100; kaolinite and halloysite have comparatively low base-exchange capacities, viz., 3-15 and 6-15, respectively; attapulgite and illite have higher base-exchange capacities, viz., 25-35 and 15-40, respectively. The clays of higher base-exchange capacitiesare particularly useful where high exchange of an organic base for the cation of theclay is desired.

Generally stated and in. accordance with illustrative embodiments of this invention, a clay, particularly one exhibiting substantial base-exchange capacity, is reacted with an organic compound, more particularly one hereinafter generally defined and referred to as an onium compound, by substitution of the clay cation, with theacation ofthe organic compound, which cation. is of a class hereinafter referred to as an onium base. The resulting compound may be used in carrying out this inventionv or may be further reacted with another. organic compound, resulting invention is not, however, restricted to the use of a reaction product of a base-salt with a claysalt, but includes the reaction product of a free base with an acid-clay.

An onium compound has been defined in Hackhs Chemical Dictionary, Second Edition, as:

"A group of organic compounds of the type RXH which are isologs of ammonium and contain the element X in its highest positive valency,

VlZZ

Where X is pentavalent as in ammonium, phosphonium, arsonium and stibonium; where X is tetravalent as in oxonium, sulfonium, selenonium and stannonium compounds; and where X is trivalent, a in iodonium compounds; and that they may be considered addition compounds of oxonium, carbonium, stibonium, c. f., -inium, -ylium.

A number of the compounds capable of reacting with clays, particularly bentonite, will be described; it is to be understood, however, that various other compounds reactable with clays, and particularly bentonite or hectorite, may be employed. These may include salts of aliphatic, cyclic, aromatic, and heterocyclic amines, primary, secondary, and tertiary amines and poly amines, also quaternary ammonium compounds, as well as other monovalent or polyvalent onium compounds, such as triphenylalkyl phosphoniumarsonium-stibonium-halides, diall y1, or arylsulphonium and selenonium halides and pyrones, such as 2,5-dimethyl gamma pyrone hydrochloride.

Untreated sodium bentonite in contact with water absorbs large quantities of the water and swells, forming a gel. This swelling has been attributed to the lamellar structure of the clay mineral and to adsorption of water molecules onto surfaces of the mineral sheets, thus giving rise to a separation of the sheets as the oriented water layers build up to an appreciable depth. If the surfaces of the clay laminae contain organic matter, as by the process of base-exchange with an organic base, the ability of water molecules to be adsorbed is eliminated, and the clay no longer exhibits its former swelling capacity in water. Thus Wyoming bentonite, for example, which is essentially the sodium salt of montmorillonitic acid, is capable of reacting with organic bases or their salts, e. g.:

or more readily The resulting dodecylammonium bentonite is visualized as consisting of clay mineral laminae with dodecylammonium groups fairly regularly distributed over the surfaces and attached by means of the substituted ammonium groups, with the hydrocarbon tails extending out over the crystal surfaces. Such a material is now organophilic rather than hydrophilic and as such exhibits in organic liquids some of the characteristics which the untreated clay exhibited in water; for example, it will swell in many organic liquids and will form stable gels and colloidal dispersions. Such gels are visually homogeneous and often transparent or translucent. They are thermally stable up to the boiling point of the liquid phase and show little tendency to flow or run when heated. The more dilute systems which are more or less liquid have viscosity 4 much higher than those of the liquids themselves, and in most cases exhibit thixotropy characteristic of the analogous bentonite-water system.

The modified clay is one which forms a gel in a surface coating vehicle and can therefore be readily incorporated with a vehicle and the pigment Or ink base. This can be accomplished by adding the modified clay to the vehicle, which then forms a gel therein. The pigment or ink base can thereafter be added. However, the modified clay can be added to a paint or ink including the pigment or ink base and a vehicle. In each case it will perform its desired function of controlling the viscosity or thickening of the vehicle and of keeping the pigment or ink base in suspension. The percentage of modified clay which should be used depends upon the character of the surface coating and of the vehicle and the percentage of the pigment or ink base and surface coating; generally, however, the amount can be from 1 to pounds per 100 gallons of the finished surface coating.

The situation is analogous to the above if the element X of the onium compound is other than nitrogen. The onium compound, should, however, be such that, for example, a resultant onium-bentonite will have substantial swelling properties in organic liquids. Such swelling characteristic may be determined by introducing 2' grams of the onium-bentonite product in 100 milliliters of nitrobenzene and noting the amount of swelling in milliliters. Thus in the case of amine-bentonite products, the employment of salts of aliphatic amines, including the octylamine, will not produce an amine-bentonite product showing a swelling of over 7.2 ml.; however, the dodecylamine bentonite product will show a swelling of from 27 ml. to ml. There is generally a distinct region of increase of swelling with amine-bentonites in which the amine has in excess of 10 carbon atoms in the carbon chain, such swelling being generally in excess of 25 ml. These products may well be called high-swelling onium-bentonites.

The ratio of the onium compound, such as, for example, an amine compound to bentonite, may be varied within certain limits in converting the bentonite to the organophilic condition. In general, it is satisfactory to react the amine salt with the bentonite in the ratio of 100 milliequivalents of amine salt to 100 grams of bentonite, which is approximately the base-exchange capacity of the standard highly swelling bentonites. Typical values of swelling on the above basis are listed below for a series of dodecylammonium-bentonites, in which the ratio of amine to bentonite was varied over wide limits:

Amine/bentonite. 50me./ 200 300 Swelling in nitrobenzene,ml. -i 27.3 43.0 65.3 47.5 30.0 20.5 1.5.5

base-exchange with the clay, will completely cover the surface of the mineral, or to substitute the proper aliphatic chain in a 'polyammonium base. It has been found that a. base whose hydrophilic radical has a linear dimension of .at least 14 angstrom units or molecular area of at least 70 square angstrom units is suitable. For example, a primary amine with a chain of carbon atoms, e. g., decyl amine, will substantially fulfill the requirements of covering the clay surface. An excess of organic matter as occasioned by use of an amine of area greater than 14 linear or 70 square angstrom units, as for example octadecylamine, is not detrimental to the gelling properties of the amine-bentonite composition. Good results, for instance, have been obtained with primary amines having hydrocarbon chains of twelve or more carbon atoms.

The type of clay material to be usedmay vary with the intended use. For optimum gelling properties, it is best to use a bentonite which exhibits good gelling properties in water. However, some non-swelling clays when converted to the onium salt form will swell in organic liquids and give rise to thixotropic colloidal dispersions.

It is to be understood that when reference is made to basic organic onium compounds such as amines, it is implied that beforereacting with the clay by base-exchange, the amine is converted to the onium form either" by the addition-of acid or by reason of the fact that some part of themorganic base in the naturally occurring clay consists of hydrogen.

In the preparation of organic gels, various methods may be followed. If it is desired to pre- Y pare a gel free from abrasive impurities, it may be advantageous to start with a dilute aqueous dispersion of bentonite and allow the non-bentonite impurities to settle out, thereafter reacting with the purified bentonite a salt of the desired amine or other basic organic compound. The flocculated onium bentonite is then filtered out, dried, ground and mixed with the organic liquid which is to be bodiedup. For rapidly accomplishing dispersion of the onium bentonite in the organic liquid, it is often advantageous to heat the mixture and pass it through a multiple-roll mill such as a paint mill, although this is not necessary for some combinations.

\ll/hereimpurities associated with the clay are of no consequency, it is often sufficient merely to add the dry clay to the organic liquid containingsufiicient aminev salt or other salts of basic organic compound to more or less. completely react with the clay. The gelling effect is thus enhanced by converting the. amine to the salt form,

or any of the other basic organic compounds to the onium form, either before or after the addi-- tion ofthe clay, by introduction ofan acidsuch as'hydrochloric or acetic acid. Further,it is also feasible to prepare a dry mixture, to be used in gel formation, by mixing the amine with dry clay and then mixing in the requisite amount of an acid, such as acetic, or by mixing the amine.

salt'with the dry clay, thereafter adding the dry amine-bentonite mixture to the liquid with which it is desired to produce a gel.

The vehicles which may beemployed are the following: (1) Oxygen convertible vehicles: A. Drying oils, raw or heat processed; soybean oil,

linseed oil, dehydrated castor oil, oiticica oil,

China-wood or tung oil; B. Drying oil modified varnishes: oleoresinous varnishes, drying oil modified alkyds, drying oils, copolymerized with unsaturated hydrocarbons; (2) Thermal conchloride.

mate, iron blue, copper phthalocyanine blue; B,

Others: organic toners and dyes, carbon black, bone" black; (3) Extenders: whitings, talc, barytes diat. silica, China clay mica.

Further examples of preparing onium-clay. are

the following:

Example A.167 lbs. of Wyoming bentonite was dispersed in 500 gallons of water and the slurry centrifuged, to. remove nonclay impurities. To the centrifugeddispersion. was added 100 gallons of an aqueous solution containing 29.5 lbs. of commercial octadecylamine and 5.7 lbs. of glacial acetic acid. The fiocculent precipitate which formed was washed to remove soluble salts,- filtered, dried at a temperature-below 175-'F. and

pulverized.

Example B.l67 lbs. of Wyoming bentonitew'as dispersed in 500' gallons of Water and centrifuged. The efiluent was mixed with 100 gallons of a solution of 74.7 lbs. of active dimethyldioctadecylammonium chloride. The iiocculent precipitate was washed, filtered, dried and pulverized.

Example (Jr-335 lbs. of magnesium bentonite from Hector, California, was dispersed in 500 gallons of water and centrifuged. The effluent was mixed with gallons of a solution of 74.7 lbs. of 75% active dimethyldioc'tadecylammonium The fiocculent' precipitate was washed, filtered, dried and pulverized.

The following examples illustrate embodiments of this invention:

EXAMPLE I 2750 g. of a Wyoming bentonitewas dispersed in 70 liters of water and the slurry allowed topound of this powder was ballmilled with 20 pounds of linseed oil to produce a viscous liquid exhibiting thixotropy, for use as a paint vehicle.

EXAMPLE II A paint of the following composition was prepared:

Pigment, 71.67 vehicle, fi oo z, white lead 34% AA linseed oil 31% pale heat bodied linseed oil 3%.dricr 32% thinner Paint N 1 2 3 Hardness in can, 21 da Settling in can, 21 days In the above table, the term consistency is a measure of the gram weight necessary to give 200 revolutions per minute in a Kreb Modified Stormer viscosimeter at 25 C.

EXAMPLE III Triphenyl-lauryl phosphonium bromide was prepared by refluxing a mixture of equivalent weights of triphenylphosphine and lauryl bromide. After six hours the reaction mixture was cooled and dissolved in alcohol. To a dispersion of 50 g. of Wyoming ben'tonite in one liter of water was added an alcohol solution of 0.05 mol of the phosp-honium base. Upon bringing the pH of the slightly basic dispersion to about 4 with dilute hydrochloric acid, the bentonite complex flocculated, was filtered, washed, dried, and ground. 2 g. of this powdered product, placed in 100 ml. of nitrobenzene in a graduate, swelled to a translucent yellow gel occupying a volume of 66 m1. Mild agitation was suificient to disperse the gel to a stable translucent thixotropic solution. This bentonite compound Was found to be suitable as a paint-thickening agent.

EXAMPLE IV One-tenth mol of didodecyl ethyl sulfonium bromide is dispersed in one liter of water, and this is then mixed by agitation with 400 cc. of a 2 suspension of Wyoming bentonite. After one hours standing, it is filtered, dried, and ground. The resulting long-chain bentonite compound thus obtained may be incorporated into a paint vehicle, with a resulting paintthickening.

EXAMPLE V The process of Example IV is carried out except that one-tenth mol of decyl-triphenylarsonium halide is used instead of didodecyl ethyl sulfonium bromide.

EXAMPLE VI The process of Example IV is carried out except that one-tenth mol of decyl-triphenylstibonium halide is used instead of didodecyl ethyl sulfonium bromide.

EXAMPLE VII The process of Example IV is carried out ex-- cept that one-tenth mol of didodecyl-gammapyrone is used instead of didodecyl ethyl sulfonium bromide.

EXAMPLE VIII The process of Example IV is carried out except that one-tenth mol of didodecyl ethyltelluronium. chloride is used instead of didodecyl ethyl sulfonium bromide.

EXAMPLE IX Paint with oleoresinous vehicle Parts Titanium calcium pigment 28.0 Zinc oxide 7.0 25% phenolic resin-tung oil varnish 35.0 Paint thinners and driers 30.0

Consistency: 200 grams Consistency: 280 grams, following the addition of 5 lbs. per 100 gallons of the product of Example A.

EXAMPLE X Paint with soybean oil modified alkyd resin solution Parts Iron oxide 12.5 Lead chromate 14.5 Lampblack 4.0

Soybean oil modified alkyd 60% oil fatty acids 30.0 Paint thinners and driers -1 39.0

Consistency: 145 grams Consistency: 212 grams, following the addition of 3 lbs. per 100 gallons of the product of Example A.

EXAMPLE XI Urea baking coating black Parts Coconut oil modified alkyd resin 8.0 Butylated urea formaldehyde resin 8.0 Carbon black 2.5 Diatomaceous silica 15.0 Paint thinners 66.5

Consistency: 67 grams Consistency: 94 grams following the addition of 2 /2 lbs. per 100 gallons of the product of Example A.

EXAMPLE XII Nitrocellulose lacquer black Parts Nitrocellulose, dry weight 10.0

Castor oil modifier alkyd resin 12.0

Dibutyl phthalate plasticizer 2.7

Lacquer solvents 73.3

Carbon black 2.0

Consistency: grams Consistency: 163 grams, following the addition of 6 lbs. per gallons of the product of Example A.

EXAMJPLE XIII Clear ethylcellulose coating Parts Ethylcellulose 12.0

Raw castor oil 1.0

Lacquer solvents 87.0

9 Consistency: 65 grams Consistency: thick gel following'the'addition of '15 lbs. per 100 gallons of the product of xainple B.

EXAMPLE XIV Asphalt base vehicle coating Parts Asphalt base vehicle 20.8 Paint thinners 30.2 Calcium carbonate 24.0 Barytes 25.0

100.0 Consistency: 165 grams Consistency: thick thixotropic gel following the addition of 3 lbs. per 100 gallons of the product of Example B.

EXAMPLE XV Parts Lithopane l 52.87 Titanium. dioxide 8.52 Raw linseed. oil 29.40 Heat bodied linseed oil 3.13 Thinners and driers 6.38

Consistency: 222 grams Consistency: 480 grams fOllOWlllg the addition of I 8 lbs. per 100 gallons of the product of Example C.

The invention having thus been described, what is claimed is:

1. A paint, comprising a pigment base suspended in an organic paint vehicle, together with a suspending medium embodying a cation modified clay, originally exhibiting a substantial baseexchange capacity, in which the clay cation has been replaced by a substituted cation of the class exchange capacity, in which the clay cation has been replaced by a substituted onium ammonium cation and which forms a gel in the vehicle and has a substantial gel characteristic therein.

3. A process of preparing a paint, comprising treating an organic paint vehicle and a pigment base, with an onium cation-modified bentonite which forms a gel in the vehicle and has a substantial gel characteristic therein and combining the resulting vehicle and base.

4. A process of preparing a paint, comprising incorporating a cation modified clay, originally exhibiting a substantial base-exchange capacity, in which the clay cation has been replaced by a substantial cation of the class of onium bases consisting of ammonium, phosphonium, sulfonium, arsonium, stibonium, oxonium, and telluronium bases, with a pigment base in an organic paint vehicle.

5. An organic coating vehicle having colloidally dispersed therein to an amount sufficient to substantially increase the viscosity thereof, a cation-modified clay, originally exhibiting a substantial base-exchange capacity, in which the clay cation has been replaced by a substituted cation of the class of onium bases consisting of arm 10 monium, phosphonium, sulfonium, arsonium, stibonium, oxonium and telluroniumbases, to an extent suflicient to form with the clay anion an organophilic clay and which forms a gel in the vehicle and has a substantial gel characteristic therein.

6. An organic coating vehicle having colloidally dispersed therein, to an amount sufficient to substantially increase the viscosity thereof, a cation-modified clay, originally exhibiting a substantial base-exchange capacity, in which the clay cation has been replaced by a substituted cation of the class of onium bases consisting of ammonium, phosphonium, sulfonium, arsonium, stiboniuin, oxonium and telluronium bases, to an extent sufficient to form with the clay anion an organophilic clay and which forms a gel in the vehicle and has a substantial gel characteristic therein, to the extent that 2 grams swell to at least 25 milliliters in nitrobenzene.

7. An organic coating vehicle having colloidally dispersed therein, to an amount suflicient to substantially increase the viscosity thereof, a cation-modified clay, originally exhibiting a substantial base-exchange capacity, in which the clay cation has been replaced by a substituted cation of the class of onium bases consisting of ammonium, phosphonium, sulfonium, arsonium, stibonium, oxonium and telluronium bases and with a hydrophobic radical having a linear dimension of at least 14 Angstrom units, to an extent suflicient to form with the clay anion an organophilic clay and which forms a gel in the vericle and has a substantial gel characteristic therein.

8. An organic coating vehicle having colloidally dispersed therein, to an amount sufficient to substantially increase the viscosity thereof, a cation-modified clay, originally exhibiting a substantial base-exchange capacity, in which the clay cation has been replaced by a substituted cation of the class of onium bases consisting of ammonium, phosphonium, sulfonium, arsonium, stibonium, oxonium and telluronium bases and with a hydrophobic radical having a molecular area of at least '70 square Angstrom units, to an extent sufficient to form with the clay anion an organophilic clay and which forms a gel in the vehicle and has a substantial gel characteristic therein.

9. An organic coating vehicle having colloidally dispersed therein, to an amount suificient to substantially increase the viscosity thereof, a cation-modified clay, originally exhibiting a substantial base-exchange capacity, in which the clay cation has been replaced by a substituted cation of the class of onium bases consisting of ammonium, phosphonium, sulfonium, arsonium, stibonium, oxonium and telluronium bases and with a hydrophobic radical having at least 10 carbon atoms in a chain, to an extent sufiicient to form with the clay anion an organophilic clay and which forms a gel in the vehicle and has a substantial gel characteristic therein.

10. An organic coating vehicle having colloidally dispersed therein, to an amount sufficient to substantially increase the viscosity thereof, a cation-modified montmorillonite in which the clay cation has been replaced by a substituted cation of the class of onium bases consisting of ammonium, phosphonium, sulfonium, arsonium, stibonium, oxonium and telluronium bases, to an extent sufficient to form with the clay anion an organophilic clay and which forms a gel in 11 the vehicle and has a substantial gel characteristic therein.

11. A paint, comprising a pigment base suspended in an organic vehicle, having colloidally dispersed therein to an extent sufficient to substantially increase the viscosity thereof, a cation-modified clay, originally exhibiting a substantial base-exchange capacity, in which the clay cation has been replaced by a substituted cation of the class of onium bases consisting of ammonium, phosphonium, sulfonium, arsonium, stibonium, oxonium and telluronium bases, to an extent sufiicient to form with the clay anion an organophilic clay and which forms a gel in the vehicle and has a substantial gel characteristic therein.

12. An ink, comprising an ink base suspended in an organic vehicle, having colloidally dispersed therein to an extent suflicient to substantially increase the viscosity thereof, a cation-modified clay, originally exhibiting a substantial base-exchange capacity, in which the clay cation has been replaced by a substituted cation of the class of onium bases consisting of ammonium, phosphonium, sulfonium, arsonium, stibonium, oxonium and telluronium bases, to an extent sufficient to form with the clay anion an organophilic clay and which forms a gel in the vehicle and has a substantial gel characteristic therein.

13. An organic coating vehicle having colloidally dispersed therein to an amount suflicient to substantially increase the viscosity thereof, an organophilic swelling ammonium bentonite having a hydrophobic radical with a molecular area of at least '70 square Angstrom units.

14. An organic coating vehicle having colloidally dispersed therein to an amount suflicient to substantially increase the viscosity thereof, an organophilic normal alkyl ammonium bentonite having an organic radical with at least 12 carbon atoms in a straight chain.

15. An organic coating vehicle having colloidally dispersed therein to an amount suflicient to substantially increase the viscosity thereof, an organophilic octadecyl ammonium bentonite..

16. An organic coating vehicle having colloidally dispersed therein to an amount sufficient to substantially increase the viscosity thereof, an organophilic dodecyl ammonium bentonite.

1'7. An organic coating vehicle having colloidally dispersed therein to an amount sufficient to substantially increase the viscosity thereof, an organophilic phosphonium bentonite having a hydrophobic radical with at least 10 carbon atoms in a straight chain.

18. An organic coating vehicle having colloidally dispersed therein to an amount sufficient to substantially increase the viscosity thereof, an organophilic sulfonium bentonite having a hydrophobic radical with at least 10 carbon atoms in a straight chain.

19. An organic coating vehicle having colloidally dispersed therein to an amount suflicient to substantially increase the viscosity thereof, an organophilic oxonium bentonite having a hydrophobic radical With at least 10 carbon atoms in a straight chain.

GEORGE L. RA'ICLIFFE.

No references cited. 

1. A PAINT, COMPRISING A PIGMENT BASE SUSPENDED IN AN ORGANIC PAINT VEHICLE TOGETHER WITH A SUSPENDING MEDIUM EMBODYING A CATION MODIFIED CLAY, ORIGINALLY EXHIBITING A SUBSTANITAL BASEEXCHANGE CAPACITY, IN WHICH THE CLAY CATION HAS BEEN REPLACED BY A SUBSTITUTED CATON OF THE CLASS OF ONIUM BASES CONSISTING OF AMMONIUM, PHOSNIUM AND TELLURONIUM, ARSONIUM, STIBONIUM, OXONIUM AND TELLURONIUM BASES, AND WHICH FORMS A GEL IN THE VEHICLE AND HAS A SUBSTANTIALGEL CHARACTERISTIC THEREIN. 